Treatment of copper-nickel pyrrhotite.



UNITED STATES PATENT OFFICES WOOLSEY MQALPINE JOHNSON, OF HARTFORD, CONNECTICUT. ASSIGNOR TO THE CONTINUOUS ZINC FURNACE COMPANY, OF HARTFORD. CONNECTICUT, A COE- PORATION OF CONNECTICUT.

TREATMENT OF COPPER-NICKEL PYRRHOTITE.

No Drawing.

To all whom it may eonr'ern Be it known that I, \VOOLsnr MCA. JOHN- sox, a citizen of the United States, residing at Hartford, in the county of .llartford and State/oi Connecticut, have invented certain new and useful Improvements in Treatment ol (.opper-Niekel Pyrrhotite, of'which the following is a full, clear, and exact description, such as will enable others skilled in the, art. to which it appertains to make and use the same,

This invention deals with an improved method of obtaining the valuable constituents from ores which have uttered eonsiderable dilticulty under such metallurgieal treatments as have hitherto been available. (ertain of the commercially nan-e important 'elmracteristics of this invention prominently appear in its utilization for the reduction of coppeeuiekel pyrrhotite ores containing a. proximately if] (.u, 4% Ni. Fe, 38% h, .10 oz. to .05 oz. lt, Pd, and Ag. and therefore it will sutliee to disclose this invention by way of a detailed description of the proposed treatment of this typical ore.

()ne object within the contemplation of this invention is to render available a proeeFs composed of a number of essentially practieal steps so seleeted, devised and interrelated as to eonstitute a eommereially economical system admirably adapted for the treatment of ores ol' the type represented.

.\nolln r ohjeet is to formulate a novel method whereby the valuable metals may be obtained at a reasonable. expense from p rodllels rich in sulfur and other elements, as for example: a matte containing approximately Elf)? Nifi: 2% Ni sy-l fl ii u S- 1% (p 9: 5% FPS. and .15 07.. ol" Ag, Pt. and ld.

The invention a-eeoriliugly consists in the several steps and the relation and order of one or more of sllell stepswith relation to eaeh ol' the others then .I', \vllieh will be exemplified in the hereinafter disclosed process, and the seope ol' the application of which will lie indicated in llll following elaims.

(out inning now by way of a. more detailed deseription ol' the preleri d illustrative embodiment ol this invention, it will he assumed that the ore to he treated is u nickeli-opper pyrrhotite. eonstituted somewhat. as Follows: 45% Fe: 3%; H: '1; Ni; 2% (-u; from tLltl oz. to no? oz. lt plus ld plus i}g;

Specification of Letters Patent.

-pplication filed October 22, 1913.

Patented Aug. 28, 1917. Serial No. 796,568.

and the balance gangue. As a preliminary step, this ore. will be subjected to the well known treatment of heap-roasting to reduce the sulfur, and then worked up by blast-furnace smelting and converting to the so-ealled S01. matte which is approximately represented by 52% Ni; ifijt C11; 19% S; lfi (0; lit Fe, and the balance gangue.

The next step will consist in cupolasmelting 80% matte with from 40% to crude Na sO, auda large excess of coke under strongly reducing conditions so as to produce a reduction of the sodium sulfate yielding sodium sulfid which dissolves the copper sultld and enables the so called tophottoms" separation to he made. The reduction is assumed to take place in accordauee with this equation:

b21 50 plus CUE 2 plus Na s plus 211760 plus 3160,.

The tops carry a large percentag of the copper (70% to vlily/t) and the 0ttoms" a. large percentage of the nickel. ThlS is repeated'two or three times, the topsfro i the seeond or tlurd smelting being run into' the furnaces giving the first and second treatments respectively, finally yielding a product composed as follows: 95% Ni S;2% Na S; 1.5% (11 5; 13 00 {70 FeS, and .15 oz. of Ag plus lt plus Pd.

The tops resulting from the foregoing treatment are smelted for copper by regular and well known methods. The rich complex nickel-bearing matte resulting from the cupola-smelting is crushed or otherwise brought into ranular form and subjected to the action 0 ehlorin gas at a temperature of from 225 C. to 275 (3., suitable receptacles being used. The. metals will be changed from sulfur eompounds into chlorids, and the sulfur will he volatilized in the form of SCI which may be condensed by means of water in a. coke tower.

By leaching the residue from thechloridizing receptacle, the various valuable metals will he brought into solution as ehlorids of Ni, (.o. (11, Fe, Pd, Pt, and Na. Such silver eldorid as may reu aiu undissolved with the matte residue may if desired he recovered In usual methods. though ores or products of the general eharaeter rf that herein dotailed seldom contain enough silver to warrant its recovery. The metals other than Ni, Fe and Co may then be removed from the solution of chloride in various equivalent ways; for example; (a) by electrolysis, using an insoluble anode, in a 1% acid solution; 6) precipitation by H 8 or Na s in an aci solution; (a) cemcntation on metallic nickel; but preferably by oementation on scra iron. The Cu, Pt, and Pd are thus obtained in a condition such that their further isolation is exceedingly easy, and may be Worked up according to known methods or soldto a copper refinery.

The resultant solution now contains Ni, Co, and Fe as chlorids and may be freed from the latter two by treating with blcaclr ing powder and Na CU or by chlorin gas and N aOH or N a 00,, The cobalt and iron will thereupon be precipitated as hydrates--- Co ()ll),, and' 'Fe,(Oll),,-a1nd may be separated by first dissolving these hydrates and carefully precipitating the iron by annlvtically exact amounts of bleaching pow in and Na co or chlorin gas and lCuOH.

The solution of lli'Cl obtained by the above is contaminated only by K210i and preferably will be treated by e aporation and crystallization to fused NiUl This is then placed in a retort and While at a full red heat subjected to the action of Water gas or other source of hydrogen, and thereby reduced to metallic nickel; the reduction being promoted ifdcsired by mixing with pmvdercil coal, The reduction is simple and takes place as 'Eollon's:

NiCl plus fi z-Ali plus QHCL This product is then obtained in the shape of metallic nickel ingots of commerce by smelting in an open hearth furnace.

Viewed in the light of current knowledge and without the necessity of further elaboration. the foregoing disclosure will he sufiiciently suggestive and otherwise enable those skilled in the art to easily devise certain interchangeably available embodiments and utilizations o this invention which, although perhaps calculated to seem dissimilar in one or more respects, from that herein shown, would nevertheless involve the ideas and utilities which, from the aspect from the prior art, are characteristic of the spirit of this invention and which there-- fore, should and accordingly are intended to fall within th contemplation of the lullowing claims; l, thercfore, i'lesire that all matter in the foregoing disclosure shall be interpreted as purely illustrative and not in a limiting sense, as it will be clear that the various stepsand operations herein (insci-ilicd may be identified by the use of various more or less arbitrary terms and that the terminology employed is descriptive rather than limiting.

water; then recovering the copper and precious metals from said solution; then precipitating the iron and cobalt as bydrates; then re-dissolving such hydrates and precipitating the cobalt only; and extracting the nickel from its solution.

2. A process of the nature disclosed for treating products containing copper, nickel, iron and precious metals together with a relatively small amount of sulfur, consisting in subjecting said product in crushed ful in to'the action of chlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultant metallic chlorids in Water; then frfiu-r;!'ing the copper and precious mctazs tics said solution by cementatiou on scrap iron; then precipitating the iron and cobalt as hydrates; then redissolving such hydrates and precipitating the cobalt only; and extracting the nickel from 1ts solution.

3. A process of the. nature disclosed for treating prod cts containing copper, nickel, iron and precious metals together with a relatively small amount of sulfur, consisting in subjecting said. product in crushed form to the action of chlorin gas in closed chumbers to volatilize out the sulfur; then li:-;- solving the resultant metallic ClllOllflS in Water; then reco ering the copper and precious metals from said solution; tin-n precipitating the iron :and cobalt us bydrates; then re-dissolving such hydrates and precipitating the cobalt only; and extract lug t e nickel from its solution by cvaporation and crystallization to obtain NiCl; and the reducing such salt in a retort with a source of hydrogen.

4. A process of the nature disclosed in: treating products containing copper, nickel, iron and precious metals together with a relatively small amount of sulfur, consisting in, subjecting saiil product in crushed form to the action of chloriu gas in cl xv i chambers to volatilize out the sulfur; tbcn dissolving the resultant metallic chloruls in water; then recovcrin v the copper and procious metals from said solution; then pro cipitating the. iron and cobalt as hydrates; by treating with a basic salt and a source. of chlorin; then malls-solving such byiilratcs and, precipitating the cobalt only; and extracting the nickel from its solution.

5. A. PIU'..GSS of the nature disclosed for treating products containing copper, nickel, iron and precious metals together with a relatively small amount of sulfur, consisting in subjecting said product in crushed form to the action of ('hlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultant Inetallic chlorids in water; then recovering the copper and pre cious metals from said solution; then precipitating the iron and cobalt hydrates; then separating the iron and cobalt by redissolving and adding a suitable agent exactly predetermined amounts adapted 'to precipitate the iron only as a hydrate; then re-dissl'ilring such hydrates and precipitating the co alt only; and extracting the nickel from its solution.

6. A proc ot? the nature disclosed for treating products containing copper, nickel, iron and precious metals together with a. relatively small amount ol sulfur, consisting in subjecting said prodiu-t in crushed form to the action oil chlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultant metallic chlorids in Water; then I'QQOVBllllg the copper and precious metals from said solution by cementation on scrap iron; then precipitating the iron and cobalt as hydrates; then re-(lissolving such hydrates and precipitating the cobalt only; and extracting the nickel from its solution by evaporation and crystallization to obtain MCI, and the reducing such salt in a retort with a source of hydrogen.

7. A process of the nature disclosed for treating products containing copper, nickel, iron and precious metals together with a relatively small amount of sull'ur, consisting in subjecting said product in crushed form to the action of ehlorin gas in closed chambers to volatilize out. the sulfur; then dissolving the resultant metallic chlorids in water; then recovering the-copper and pro-- cious metals from said solution by cementution on scrap iron; then precipitating the iron and cobalt hydrates by treating with a basic salt and a source of chlorin; then realissolvin r such hydrates and precipitating the cobalt only; and extracting the nickel from its solution.

8. A process of the nature disclosed for treating products containing copper, nickel, iron and precious metals together with a relatively small amount of sulfur, consisting in subjecting said product in crushed form to the acti n ol vhloriu gas ill closed chamhers to \olulill'laout the sulfur; then dis whine the. resultant metallic rhlorids lll water; then recovering the opper and preeious nu-lals l'roui said solution by mum-Illution on s rap iron; th n pre ipltating the in"! and cobalt as hydrates: then separating the iron and. cobalt by 1 'e--dissolvin; and adding a suitable agent exactly predelen mined amounts adapted to,prec1p|tato the iron onl as a hydrate; then re-dissolving such by! rates and precipitating the cobalt only; and extracting the nickel from its solution. I

9. A process of the nature disclosed for treating products containing copper, nickel, iron and precious metals together with a relatively small amount of sulfur, consisting in subjecting said product in crushed form to the action of chlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultant metallic chlorids in water; then recovering the copper and precious metals from said solution h cemeiitation on scrap iron; then precip1tating.the .iron and cobalt as hydrates by treating with a basic salt and a source of chlorin; then re-dissolving such hydrates and precipitating the cobalt only; and extracting the nickel from its solution, by evaporation and crystallization to obtain NiCl and the reducin such salt in a retort with a source of lryr rogen.

ID. A. process of the nature disclosed for treatingprodu b ontaining copper, nickel, iron and precious metals together with a relatively small amount of sulfur. consisting in subjecting said product in crushed form to the action of chlorin gas in closed cham-. hers to volatilize out the sulfur; then dissolving the resultant metallic chlorids in water; then recovering the copper and precious metals from said solution by cementution on scrap iron; then precipitating the iron and cobalt as hydrates; then separating the iron and cobalt by rc-dissolvin and adding a suitable agent exactly predetcrmined amounts adapted to precipitate the iron only as a hydrate; then ire-dissolving such hydrates and precipitating the cobalt only; and extracting' the nickel from its solllllltm by evaporation and crystallization to obtain NiCl and the reducing such salt in a retort with a source of hydrogen.

11. A process of the nature disclosed l'nl' treating products containing copper, nickel, iron and precious metals together with a relatively small amount of sulfur, ronsistnu; in subjecting said product in crushed form to the action of ehloriu gas in closed rluuuhersto volatilize out the sulfur; then dissolving the.resultantmetallic ehlorids in water: then recovering the copper and previous metals from said solution by cementution on serap iron; then precipitating the iroiraml cobalt as hydrates by trim-ding with a basic salt and a source of chlorin; then separating the iron and cobalt by re-dissolving and adding a suitable agent exactly |u'tuloterniiued amounts adapted to precipitate the iron old as a hydrate; then realissolvinc' such hydrates and precipitating the cobalt only; and extracting the nickel from its solution by evaporation and crystallizelion to obtain NiOl and then reducing such salt in a retort with a source of hydrogen.

12. A process of the nature disclosed for treating sulfur-bearing ores containing cop per, nickel, iron and preciousmetals consist ing in heap-roasting the ore to reduce the sulfur content; then blast-furnace smelting said roasted-ore into a matte; then reducing said matte with coke and salt-cake by cupola-smelting and separating out the resultant nickel-bearing matte; then subjecting said 'mattein crushed form to the action of chlorin gas in closed chambers to, volatilize out the sulfur; then dissolving the resultant metallic chlorids in water; then recoverin the copper and precious metals from sai solution, and then treating the residual solution to precipitate the iron and cobalt as hydrates; and then treating the residual solution of nickel chlorid to obtain the nickel therefrom.

13. A process of the nature disclosed for treating sulfur-boa ring ores containing copper, nickel iron and precious metals consisting in heap-roasting the ore to reduce the sulfur content; then hlast-furnace smeltingz said roasted ore into a matte; then re ducing said matte with ('Olit? and saltcalie lay cupola-smelting and separating out the resultant nickelbearing matte; then subjecting said matte-inrlmshed form to the action of chlorin gas in closed chambers to volatilize out the sulfur then dissolving the resultant metallic chloride in water; then recovering the copper and precious metals from said solution hy cementation on scrap iron; then precipitating the iron and cobalt as hydrates; then re-dissolving such hydrates and precipitating the cobalt only; and extracting the nickel from its solution.

14-. A process of the nature disclosed for treating sulfur-bearing ores containing copper nickel, iron and precious metals com sisting in heap-roastin the ore to reduce the sulfur content; then last-furnace smelt ing said roasted ore into a matte; then reducing said matte with coke and salt-cake by cupola-smelting and separating out the resultant nickcLbearing matte, then subjecting said matte in. crushed form to the action of chiorin gas in closed chambers 'to volatilize out the-sulfur; then dissolving the resultant metallic chlorids in Water; then recovering the copper and precious metals from said solution; then precipitating the iron and cobalt as hydrates; then Y's-dissolving such hydrates and precipitatin the cohalt only; and extracting the nic el from its solution by evaporation and crystallizns tion to obtain NiC 2 and the reducing such salt in a, retort with a source of hydrogen.

15. treating sulfur-bearing ores containing copper. nickel, iron and precious metals consisting in heap-roasting the ore to reduce process of the nature disclosed for the sulfur content; then blast-furnace smelting said roasted ore into a matte; then reducing said matte with coke and salt-cake by cupola-smelting andseparatin out the resultant nickel-bearing matte; t on subjecting said matte in crushed form to the action of chlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultantmetallic chlorides in water; then recovering the copper and precious metals from said solution; then precipitating with a basic salt and a source of chlorin; then re-(lissolving such hydrates and'precipitating the cobalt only; and extracting the nickel from its solution. 30

161A process of the nature disclosed for treating sulfur-hearing ores containing copper, nickel, iron and precious metals consisting in heap-roasting the ore to reduce the sulfur content; then blast-furnace smelt- 35 lug said roasted ore into a matte; then reducing said matte with coke and salt-cake liy cupoia-smelting and separating out the resultant nickel-bearing matte; then subjecting said matte in crushed form to the action ot chlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultant metallic chlorids in water; then recovering the copper and precious metals from said solution; then precipitating the iron and cobalt as hydrates; then separating the iron and cobalt by re-dissolving and adding a suitable agent exactly redetermined amounts adapted to precipitate the iron only as a. hydrate: then re-dissolving such hydrates and precipitating the cobalt only; and extracting the nickel from its solution.

ll. A process of the nature disclosed for treating suillur-hcariup ores containing copper nickel, iron and precious metals consisting in heapuoastingz the ore to reduce the sulfur content; then blast-furnace smelting said roasted ore into a matte; then reducing said matte will: coke and salt-cake 0 by cupola-smelling and separating out the resultant nickel-hearing matte; then subjecting said mat e in crushed form to the action of ehlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultant metallic chloride in water; then recovering the cop er and precious metals from said solution y cementation on scrap iron; then precipitating the iron and cobalt as hydrates; then re-dissolving such hydrates and precipitatin the cobalt only: and extracting the niche om its solution ply evaporation and crt'stall nation to obtain if?! and the reducing such salt in a retort with a source of hydrogen. V 4

18. A process of the nature disclosed for treating 'sulfurhearing ores containing copper, nickel. iron and precious metals consistlll in heap-roasting the ore to reduce the said roasted ore into a matte; then reducing said matte with coke and salt-cake by cupol1tsmelting and separating out the resultant nickel-bearing matte; then subjectin' said matte in crushed form to the action 0 chlorin gas in closed chambers to volatilize out the sulfur; then clissolvin the resultant metallic chloride in water; t on recovering the copper and precious metals from said solution by cementatio'n on scrap iron; then pI' e cipitating the iron and cobalt as hydrates by treating with a basic salt and alsource of chlorin; then re-dissolvin such hydrates and precipitating the cube t only; and extractmg the nickel from its solution.

19. A process of the nature disclosed for trcatin sulfur-bearing ores containing cop per, nic el, iron and precious metals consistmg in heap roasting the ore to reduce the sulfur content; thenblast-furnace smelting said roasted are into a matte; then reducing said matte with coke and salt-cake by cu olasmelting and separatin out the resu tant nickel-bearin matfle; t en subjcctin said matte in crus ed form to the action 0 chlorin gas in closed chambers to volatilize out the sulfur; then dissolvin the resultant metallic chloride in water; tl en recoverin the copper and precious metals from sai solution b cementation on scra iron; then grecipitatmg the iron and co alt as hyrates; thenvseparating the iron and cobalt by re-dissolving and adding a suitable agent exactly predetermined amounts adapted to precipitate the iron only as a hydrate; then r'e-dissolving such hydrates and precipitatin the cobalt only; and extracting the nickdl from its solution. x I

20. A process of he nature disclosed for treatin sulfur-bear gorescontaining copper, nic e1, iion andpre lous metals consisting in heap-roasting the ore to reduce the sulfur into a atte; then reducing saidmatte with coke and salt-cake by cupola-smelting and separating out the resultant nickelhearing matte; then subjecting said matte in crushed form to the action of chlorin gas in closed chambers to volatilize out the sulfur; they dissolving the resultant metallic chlorids in water; then recovering thecopper and precious metals from said solution by cementation on scrap iron; then precipitating the iron and cobalt as hydrates by treating'with a basic salt and a source of chlorin; then re-dissolving such hydrates and precipitating the cobalt only; and extracting the nickel from its solution, by evaporation and crystallization to obtain N iCl and the reducing such salt in a retort with a source of hydrogen.

21. A process of the nature disclosed for treating sulfur-bearing ores containing copper nickel, iron and precious metals consisting in heap-roastin the ore to reduce the sulfur content; then b ast furnace smelting said roasted ore into a matte; then reducing said matte with coke and salt-cake by cupolasmelting and separatin out the resultant nickel-be'arin matte; t en subjecting said matte in crus ed form to the action of chlorin gas in closed chambers to volatilize out the sulfur;.then dissolving out the resultant metallic chloride in water; then recovering the cop er and precious metals from said solution y cementation on scrap iron; then recipitating the iron and cobalt as byrates; then separatin the iron and cobalt by re-dissolving and a ding a suitable agent exactly predetermined amounts adapted to precipitate the iron only as a hydrate; then re-dissolving such hydrates and precipitating the cobalt only; and extracting the nickel from its solutlon by evaporation and crystallization to obtain NiCl; and the reducing slich salt in a retort with a source of hydrogen.

22. A process of the nature disclosed for treatin sulfur-bearing ores containing copper, nic cl, iron and recious metals consisting in heap roastingt core to reduce the sul- :fur content; then blast-furnace smelting said roasted ore into a matte; then reducing said matte with coke and salt-cake by cupolasmelting and separatin out the resultant nickel-bearing matte; t en subjecting said matte in crushed form to the action of chlorin gas in closed chambers to volatilize out the sulfur; then dissolving the resultant metallic chlorids in water; then recovering the copper and precious metals from said solution by cementation on scrap iron; then precipitating the iron and cobalt as hydrates by treatin with a basic salt and a source of chlorin; tgen separating the iron and cobalt by re-dissolvingfand adding a suitable agent exactly predetermined amounts adapted to precipitate th' iron only as a hydrate; thcn re-rlissolvin iich hydrates and pi ecipitating'the cobal t only; and extracting the nickel from its solution by evaporation and crystallization to obtain NiCl and the reducing such salt in a retort with a source of hydrogen.

In testimony whereof I aflix my signature, in the presence of two witnesses.

WOOLSEY MOALPINE JOHNSON. 

